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Dec. 3, 192.9

UNITED STATES PATENT, OFFICE mrron Om NORTH, 01 AKRON, OHIO, ABBIGNOB TO THE RUBBER SERVICE LABORA- TORIES OI AKRON, OHIO, A CORPORATION OF OHIO mom ALDEHYDE DERIVATIVE OI REACTION PRODUCTS 01 annnmns AND AIINEB AND PROCESS OI MAKING SAME Io Drawing. Original application filed larch M, 1928, Serial No. 827,825. Patented February 14, 1928, I0. 1,658,151. Divided and application nled March 5, 1996, Serial 1T0. 92,816. ratent No. 1,618,958, dated larch 8, 1927. Application for reissue filed December 22, 1927. Serial No. 242,005.

This application is a division of myapplication Serial N 0. 627,325, filed March 24, 1923, which application matured into Patent No. 1,659,151, issued February 14, 1928.

My invention relates to a process of reactin ali hatic aldehydes higher than formaldehy e with condensation products of aromatic primary amines and aliphatic aldehydes, and particularly reacting acetaldehyde with the condensation product of three mols of acetaldehyde and two mols of aniline.

The invention also comprises the new materials obtained.

A method of making a compound in which 3 mols of acetaldehyde are combined with 2 mols of aniline is set forth in my Patent N 0. 1,659,152, granted February 14, 1928. The compound so produced is believed to be in the nature of, or closely related in chemical constitution to, derivatives of tetrahydroquinoline, which possesses what I choose to call a reactive methyl group, having the property of condensing with one or more molecules of an aldehyde to produce further reaction roducts.

According to the preferred mode of procedure, acetaldehyde is reacted with aniline to produce a compound inwlnch 3 mols of acetaldehyde are combined with 2 mols of aniline, as claimed in my aforementioned application Serial No. 627,326, and the material so obtained is dehydrated by evaporation at temperatures no higher than 105 (3., until the moisture content is substantially reduced. Advantageouslythe dehydration may be continued until the moisture content is approximately 2%. I have found that this dehydrated, compound will react with further aldehyde and in particularly with aliphatic aldehydes higher than formaldehyde, as acetaldehyde and still higher aldehydes. hydration of this compound to a substantial extent, at least, is necessary for obtaining optimum yields, the presence of water in substantial proportions apparently being unfavorable to the reaction of aliphatic aldehydes above formaldehyde upon this compound.

One example-of the ways in which a procdehyde is reacte ess within my invention can be carried out is the followin v 132 parts mol) of the dehydrated condensation product of acetaldehyde and aniline above described are refluxed with 79.5

arts (approximately 1.8 mols) of acet'aldeiyde for a period of about 14 or 15 hours at a temperature above the boiling point of the aldehyde, but below the boiling point of water.- The refluxing period can be reduced by use of efficient heating means. At the end of the reaction period I preferably discontinue the refluxing, and heat to a temperature of not over 105 C., to evaporate the water and remove the excess aldehyde. In order to avoid frothing and forming I may pass a current of air through the mass while the water is being eva orated. When the water has been practical y all removed it is often advantageous to heat at a somewhat higher temperature for a period of about hour or less, but in no case is it advisable to heat above about 115 C. The resinous productso obtained contains approximately 2% of moisture, is hard and vitreous, and can be readily ground and sifted.

The proportion of ingredients emplo ed in the example set forth when calculate molecular basis shows that the final product obtained results from the combination of one molecular proportion of aniline with sub-- stantially 3.3'molecular proportions of acetaldehyde. The example, then, discloses the reaction product of an aromatic primary amine with an aliphatic aldehyde containing more than one carbon atom, wherein the product formed results from the combination of the ingredients set forth in the ratio of one molecular proportion of the former to at least three of the latter.

A similar change takes place, when acetalsubstantially as disclosed above with the primary aldehyde derivative of anhydro formaldehyde aniline, or with the primary aldehyde derivative of the condensation product formed by the interaction of aliphatic aldeh'ydes, such as formaldehyde or acetaldehyde on, primary amines such as aniline, o-toluidine, m-toluidine, p-toluidine,

the xylidines, aminocymene, etc. The quanone tit of aldehyde taken to combine with the al ehyde-amine condensation product is preferably in excess of that actually required to complete the change.

Although in the example given I have specified the use of acetaldehyde on the dehy-' aldehyde With the condensation product of aliphatic aldehydes and aromatic primary amines.

I claim:

1. A hard resinous compound formed'by the action of acetaldehyde on the reaction product of 3 mols of acetaldehyde with 2 mols of aniline.

'2. The process of making a hard resinous compound, which comprises reacting acetaldehyde with the reaction product of 3 mols of acetaldehyde with 2 mols of aniline. 3. A hard resinous compound formed by the action of acetaldehyde on the dehydrated reaction product of 3 mols of acetaldehyde with 2 mols of aniline:-

' 4. The process of making a hard resinous compound, which comprises reacting acetaldehyde with the dehydrated reaction product of 3 mols of acetaldehyde with 2 mols of aniline.

5. A hard resinous compound formed by the action of acetaldehyde-on the dehydrated reaction product of acetaldehyde and aniline. 6. The rocess of making a hard resinous compound which comprises reacting acetaldehyde on the dehydrated reaction product of acetaldehyde and aniline.

7 A hard resinous compound formed by a the action of an aliphatic aldehyde higher than formaldehyde on the dehydrated reaction product of 3 mols of acetaldehyde with 2 mols of aniline. r Y

8. The )rocess of making a hard resinous compound, which comprises reacting an aliphatic aldehyde higher than formaldehyde on the dehydrated reaction product of 3 mols of acetaldehyde with 2 mols of aniline.

' 9. An aldehyde amine product obtained by the reaction'of an aliphatic aldehyde higher than formaldehyde on the reaction product of an aliphatic aldehyde and an aromatic primary amlne.

10. The process of making an aldehydeamine compound, which comprises reacting an aliphatic aldehyde higher than formaldeh do on the reaction product of an aliphatic a dehyde and an aromatic primary amine.

- 11. The process of making a resinous material, which comprises reacting acetaldehyde and aniline under conditions to produce a reevacuating water rom the product so obtained, introducing acetaldehyde into said product in the proportion of approximately 79.5 parts of acetaldehyde to 132 parts of said product, refluxing the mixture at'a temperature above the boiling point of acetaldehyde and below the boiling point of water for several hours, evacuating water, then further heating at a temperature not to exceed 115 C., and then coollng and grinding.

13. A hard resinous compound formed by.

reacting approximately 79.5 parts of acetaldehyde with approximately 132 parts of the dehydratedreaction product of 3 mols of acetaldehyde and 2 mols of aniline.

H. The process of making a hard resinous compound, which comprises reacting approximately 79.5 parts of acetaldehyde with approximatel 132 parts of the dehydrated reaction pro uct of 3 mols of acetaldehyde and 2 mols of aniline.

15. The process of preparing the aldehyde derivative of the reaction product of an aldehyde and an aromatic primary amine which comprises reacting the amine with an excess of the aldehyde in a plurality of stages substantially as described.

16. The process of preparing the acetaldehyde derivative of the reaction product of acetaldehyde and aniline which comprises reacting aniline with an excess of acetaldehyde in a plurality of stages, substantially as described. s

signature.

- CLAYTON OLIN NORTH. 

